Cyclopropanated macrocyclic ketones and lactones

ABSTRACT

The present invention is directed to novel cyclopropanated macrocyclic ketone and lactone compounds of the general formula: 
     
       
         
         
             
             
         
       
         
         
           
             wherein X is an atom or a functional group selected from the group consisting of O, N, S, R—CH, and CH2; 
             wherein R is a C1-C3 alkyl group; 
             wherein Y and W independently represent is a linear or branched alkyl or alkenyl group, optionally substituted, consisting of less than 10 and preferably less than 7 carbon atoms; and 
             wherein O is an oxygen atom, 
             and the use of these novel compounds in creating fragrances and scents in items such as perfumes, colognes, and personal care products.

RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 11/386,957, filed Mar.22, 2006, now U.S. Pat. No. 7,485,668, which is a continuation-in-partof the U.S. Ser. No. 11/105,626, filed Apr. 14, 2005, now U.S. Pat. No.7,189,881.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how differences in the chemical structuresof the molecules can result in significant differences in the odor,notes and characteristics of the molecules. These variations and theongoing need to discover and use the new chemicals in the development ofnew fragrances allow perfumers to apply new compounds in creating newfragrances.

SUMMARY OF THE INVENTION

The present invention provides novel chemicals, and the use of thechemicals to enhance the fragrances of perfumes, toilet waters,colognes, personal products, fabric care products, and the like.

More specifically, the present invention is directed to the novelcyclopropanated macrocyclic compounds, represented by the generalstructure set forth below:

wherein X is an atom or a functional group selected from the groupconsisting of O, N, S, R—CH, and CH2; wherein R is a C1-C3 alkyl groupselected from the group consisting of methyl, ethyl, propyl, andisopropyl; wherein Y and W independently is a linear or branched alkylor alkenyl group, possibly substituted, consisting of less than 10 andpreferably less than 7 carbon atoms.

Another embodiment of the invention is a method for enhancing a perfumeby incorporating an olfactory acceptable amount of the compoundsprovided above.

Another embodiment of the invention is a method for enhancing a perfumeby incorporating an olfactory acceptable amount of a compound ofstructure set forth below:

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

In Formula I above, wherein Y and W independently is a linear orbranched alkyl or alkenyl group consisting of less than 10, preferablyless than 7 carbon atoms. Suitable linear alkyl groups include methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the like. Suitablebranched alkyl groups include isopropyl, isobutyl, sec-butyl,tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, 2-ethyl-propyl,and the like. Suitable alkenyl groups include ethene, propene, 1-butene,2-butene, penta-1,3-deine, hepta-1,3,5-triene, and the like.

In a preferred embodiment, the novel compounds of the present inventionare represented by the following structures:

Those with the skill in the art will appreciate that:

the compound of Formula III is bicyclo[13.1.0]hexadecan-4-one;

the compound of Formula IV is 9-oxa-bicyclo[15.1.0]octadecan-8-one;

the compound of Formula V is bicyclo[14.1.0]heptadecan-5-one;

the compound of Formula VI is bicyclo[15.1.0]octadecan-9-one;

the compound of Formula VII is 5-oxa-bicyclo[14.1.0]heptadecan-6-one;

the compound of Formula VIII is3-methyl-bicyclo[13.1.0]hexadecane-5-one;

the compound of Formula IX is bicyclo[12.1.0]pentadecan-3-one;

the compound of Formula X is3-methyl-6-oxa-bicyclo[13.1.0]hexadecane-7-one; and

the compound of Formula XI is bicyclo[14.1.0]heptadecan-8-one.

The table below lists additional compounds derived from Formula I thatare covered in the present invention:

W Y X Compound CH₂ (CH₂)₄ CH₂ Bicyclo[7.1.0]decan-3-one CH₂ (CH₂)₅ CH₂Bicyclo[8.1.0]undecan-3-one (CH₂)₃ (CH₂)₅ CH₂Bicyclo[10.1.0]tridecan-5-one (CH₂)₅ (CH₂)₅ CH₂Bicyclo[12.1.0]pentadecan-7-one (CH₂)₅ (CH₂)₅ CH₂Bicyclo[13.1.0]hexadecan-7-one CH₂ (CH₂)₅ O4-Oxa-bicyclo[8.1.0]decan-3-one CH₂ (CH₂)₅ S4-Thia-bicyclo[8.1.0]decan-3-one (CH₂)₅ (CH₂)₅ O7-Oxa-bicyclo[12.1.0]pentadecan-8-one (CH₂)₅ (CH₂)₅ S7-Thia-bicyclo[12.1.0]pentadecan-8-one (CH₂)₅ CH(CH₂)₄ CHBicyclo[12.1.0]pentadec-8-en-7-one (CH₂)₉ C(CH₃)HCH₂ CH₂3-Methyl-bicyclo[13.1.0]hexadecane-5- one (CH₂)₉ C(CH₂CH₃)HCH₂ CH₂3-Ethyl-bicyclo[13.1.0]hexadecane-5- one (CH₂)₉ C(CH₃)HCH₂ O3-Methyl-4-oxa- bicyclo[13.1.0]hexadecane-5-one (CH₂)₉ C(CH₂CH₃)HCH₂ O3-Ethyl-4-oxa- bicyclo[13.1.0]hexadecane-5-one (CH₂)₉ C(CH₃)HCH₂ S3-Methyl-4-thia- bicyclo[13.1.0]hexadecane-5-one (CH₂)₉ C(CH₂CH₃)HCH₂ S3-Ethyl-4-thia- bicyclo[13.1.0]hexadecane-5-one (CH₂)₉ C(CH₃)HCH₂ N3-Methyl-4-aza- bicyclo[13.1.0]hexadecane-5-one (CH₂)₉ C(CH₂CH₃)HCH₂ N3-Ethyl-4-aza- bicyclo[13.1.0]hexadecane-5-one (CH₂)₈CH(CH₃) (CH₂)₃ O15-Methyl-5-oxa- bicyclo[14.1.0]heptadecan-6-one (CH₂)₈CH(CH₂CH₃) (CH₂)₃O 15-Ethyl-5-oxa- bicyclo[14.1.0]heptadecan-6-one (CH₂)₆(CH)₂CH(CH₃)(CH₂)₃ O 15-Methyl-5-oxa- bicyclo[14.1.0]heptadec-13-en-6-one

The compounds of the present invention may be prepared fromcorresponding alkenes via Simmons-Smith cyclopropanation reaction, whichis a stereospecific synthesis of cyclopropenes by treatment of olefinsZn—CU couple or diethyl zinc and methylene iodide in tert-butyl methylether as a solvent.

As described in the Examples below, compounds of Formulae III-XI may beprepared via Simmons-Smith cyclopropanation reaction from thecorresponding alkenes of the compounds set forth below:

The alkenes of Formulae XII-XX are commercially available fragranceproducts. The compound of Formula XII is cyclopentadec-4-enone and isavailable from International Flavors & Fragrances Inc., New York, N.Y.under the trade name Musk Z-4. The compound of Formula XIII isoxacycloheptadec-9-en-2-one and is available from International Flavors& Fragrances Inc., New York, N.Y. under the trade name Ambrettolide. Thecompound of Formula XIV is cyclohexadec-5-enone and is commerciallyavailable under the trade names Velvione from Givaudan and Ambretonefrom Takasago. The compound of Formula XV is cycloheptadec-9-enone andis commercially available under the trade name Civettone. The compoundof Formula XVI is oxacyclohexadec-12-en-2-one. The compound of FormulaXVII is 3-methyl-5-cyclopentadecene-1-one and is commercially availableunder the trade name of Muscenone. Preparation of3-methyl-5-cyclopentadecene-1-one is described in U.S. Pat. No.6,720,303. The compound of formula XVIII is cyclotetradec-2- and or3-ene-1-one and is available from the International Flavors & FragrancesInc. New York, N.Y. The compound of Formula XIX is12-methyl-14-cyclotetradec-9-enolide, preparation of which is describedin EP 908 455 A1. The compound of Formula XX is a cyclohexadec-3-enoneand is commercially available from Symrise under the trade nameGlobanone.

Those with skill in the art will recognize that the compounds of thepresent invention have a number of chiral centers, thereby providingnumerous isomers of the claimed compounds. It is intended herein thatthe compounds described herein include isomeric mixtures of suchcompounds, as well as those isomers that may be separated usingtechniques known to those having skill in the art. Suitable techniquesinclude chromatography such as HPLC, and particularly gel chromatographyand solid phase microextraction (“SPME”).

We have discovered that the compounds of Formulae III-X have musk,sweet, powdery, floral tones that are well suited for use as fragranceingredients.

We have also discovered that a mixture of the compound of Formula XI andits precursor, the compound of Formula XX, a mixture ofbicyclo[14.1.0]heptadecan-8-one and cyclohexadec-3-enone, possessesolfactory properties that are superior to those of the above purecompounds when taken alone. For example, the mixture ofbicyclo[14.1.0]heptadecan-8-one and cyclohexadec-3-enone at a ratio of7:3 exhibits stronger sweet floral tones than purebicyclo[14.1.0]heptadecan-8-one or pure cyclohexadec-3-enone. Thepreferred ratio of the compound of the present invention to itsprecursor is from about 1.5:1 to about 4:1. The most preferred ratio is3:1.

Another embodiment of the invention is a method for enhancing a perfumeby incorporating an olfactory acceptable amount of the compound ofstructure below:

Preparation of the compound of Formula II is described in Eugene A. Mashet al., Journal of Organic Chemistry 61, page 2743, year 1996. Thecompound of Formula II is known as bicycle[12.1.0]pentadecan-2-one.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products as well as air fresheners and cosmeticpreparations. The present invention can also be used to perfume cleaningagents, such as, but not limited to detergents, dishwashing materials,scrubbing compositions, window cleaners and the like.

In these preparations, the compounds of the present invention can beused alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk, flower scents such as lavender-like, rose-like,iris-like, carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

Olfactory effective amount is understood to mean the amount of compoundin perfume compositions the individual component will contribute to itsparticular olfactory characteristics, but the olfactory effect of theperfume composition will be the sum of the effects of each of theperfumes or fragrance ingredients. Thus the compounds of the inventioncan be used to alter the aroma characteristics of the perfumecomposition, or by modifying the olfactory reaction contributed byanother ingredient in the composition. The amount will vary depending onmany factors including other ingredients, their relative amounts and theeffect that is desired.

The level of compound of the invention employed in the perfumed articlevaries from about 0.005 to about 10 weight percent, preferably fromabout 0.5 to about 8 and most preferably from about 1 to about 7 weightpercent. In addition to the compounds other agents can be used inconjunction with the fragrance. Well known materials such assurfactants, emulsifiers, polymers to encapsulate the fragrance can alsobe employed without departing from the scope of the present invention.

Another method of reporting the level of the compounds of the inventionin the perfumed composition, i.e., the compounds as a weight percentageof the materials added to impart the desired fragrance. The compounds ofthe invention can range widely from 0.005 to about 70 weight percent ofthe perfumed composition, preferably from about 0.1 to about 50 and mostpreferably from about 0.2 to about 25 weight percent. Those with skillin the art will be able to employ the desired level of the compounds ofthe invention to provide the desired fragrance and intensity.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to standfor parts per million and g is understood to be grams. IFF as used inthe examples is understood to mean International Flavors & FragrancesInc.

Example A Preparation of Bicyclo[13.1.0]hexadecan-4-one

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 2.7 g of 94%4-cyclopentadecen-1-one and 50 ml of Methyl Tertiary Butyl Ether (MTBE)was added. The resulting mixture was stirred for 5 minutes. 21.8 ml of1.1 M Et₂Zn were added slowly. The temperature of the mixture rose to35° C. After the temperature of the mixture stabilized, 23 g of CH₂I₂were added while stirring. The mixture was heated to 60° C. In about 60minutes a first sample of the product was taken. The mixture was left toage overnight. Next morning, the mixture was quenched with saturatedNH₄Cl, aqueous layer separated and the organic layer washed with NaHCO₃.The organic layer was then dried over anhydrous MgSO₄. The gaschromatography test indicated that 74.4% of the starting alkene ketoneconverted to the cyclopropanated ketone.

The NMR spectrum of bicyclo[13.1.0]hexadecan-4-one is as follows: 0.6ppm (m, 1H); 0.7 ppm (s, 2H); 0.9 ppm (m, 1H); 1.1 ppm (s, 1H); 1.2-1.4ppm (m, 12H); 1.5 ppm (m, 5H); 1.7 ppm (m, 2H); 1.8 ppm (m, 1H); 2.1 ppm(s, 1H); 2.3-2.5 ppm (m, 3H); 3.6 ppm (m, 1H).

Example B Preparation of 9-Oxa-bicyclo[15.1.0]octadecan-8-one

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 8 g of ZnCu, 26g of CH₂I₂, 100 ml of Et₂O and 2 crystals of 12, were added and stirred.12 g of oxacycloheptadec-8-en-2-one were added to the mixture and themixture was heated to reflux. In 4 hours, first sample was taken at 35°C. The mixture was left to age overnight. Next morning, the mixture wasquenched with saturated NH₄Cl, aqueous layer separated and the organiclayer washed with NaHCO₃. The organic layer was then dried overanhydrous MgSO₄. The gas chromatography test indicated that 8.1% of thestarting alkene lactone converted to the cyclopropanated lactone.

The NMR of 9-oxa-bicyclo[15.10]octadecan-8-one is as follows: 0.0-0.2ppm (m, 1H); 0.3 ppm (s, 1H); 0.4 ppm (s, 1H); 0.5 ppm (s, 1H); 0.8 ppm(m, 1H); 1.3 ppm (s, 14H); 1.6 ppm (m, 6H); 1.8 ppm (d, 1H); 2.0 ppm (m,2H); 2.3 ppm (s, 2H); 4.1 ppm (m, 2H); 5.1 ppm (m, 1H).

Example C Preparation of bicyclo[14.1.0]heptadecan-5-one

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 2.9 g of5-cyclohexadecene-1-one and 25 ml of Methyl Tertiary Butyl Ether (MTBE)were added. 21.8 ml of 1.1 M solution of Et₂Zn in toluene was added viasyringe while stirring. 23 g (6.9 ml) of CH₂I₂ was added all at once.The mixture was heated to 60° C. and the first sample was taken. The gaschromatography test indicated that 76.3% of the starting alkene ketoneconverted to the cyclopropanated ketone. 5 ml of Et₂Zn were added to themixture and the mixture was stirred for 2 hours. A second sample wastaken. The gas chromatography test indicated that 81.6% of the startingalkene ketone converted to the cyclopropanated ketone. Another 5 ml ofEt₂Zn were added to the mixture and the mixture was stirred for 2 hours.A second third was taken. The gas chromatography test indicated that83.6% of the starting alkene ketone converted to the cyclopropanatedketone. The mixture was left to age overnight. Next morning, the mixturewas quenched with saturated NH₄Cl, aqueous layer separated and theorganic layer washed with 200 ml of brine. The organic layer was thendried over anhydrous MgSO₄.

The NMR of bicyclo[14.1.0]heptadecan-5-one is as follows: 0.2 ppm (d,2H); 0.4 ppm (s, 2H); 0.6 ppm (m, 1H); 0.7 ppm (s, 2H); 0.8 ppm (m, 1H);1.1 ppm (m, 3H); 1.2-1.5 ppm (s, 39H); 1.6-1.8 ppm (m, 11H); 2.1 ppm (s,3H); 2.2-2.7 ppm (m, 10H); 5.2-5.5 ppm (m, 2H).

Example D Preparation of Bicyclo[15.1.0]octadecan-9-one

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 3 g of9-cycloheptadecene-1-one and 70 ml of Methyl Tertiary Butyl Ether (MTBE)were added. 21.8 ml of 1.1 M solution of Et₂Zn in toluene was added viasyringe while stirring. 23 g (6.9 ml) of CH₂I₂ was added all at once.The mixture was heated to 60° C. and the first sample was taken. The gaschromatography test indicated that 77.3% of the starting alkene ketoneconverted to the cyclopropanated ketone. The mixture was left to ageovernight. Next morning, the mixture was quenched with saturated NH₄Cl,aqueous layer separated and the organic layer washed with 200 ml ofbrine. The organic layer was then dried over anhydrous MgSO₄.

The NMR of bicyclo[15.1.0]octadecan-9-one is as follows: 0.5 ppm (s,1H); 0.6 ppm (s, 2H); 1.1 ppm (d, 2H); 1.3 ppm (s, 11H); 1.4 ppm (s,8H); 1.6 ppm (s, 4H); 2.4 ppm (m, 4H).

Example E Preparation of 5-Oxa-bicyclo[14.1.0]heptadecan-6-one

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 16 g of ZnCu,200 ml of Methyl Tertiary Butyl Ether (MTBE) were added and 3 crystalsof I₂ were added and stirred. 104 g of CH₂I₂ was added while stirring.The mixture was heated maintained at 60° C. 48 g ofoxacyclohexadec-12-en-2-one was added dropwise over 90 minutes. Inanother 20 minutes a first sample was taken. The gas chromatography testindicated that 45.9% of the starting alkene lactone converted to thecyclopropanated lactone at this point. In 2 hours a second sample wastaken. The gas chromatography test indicated that 62.1% of the startingalkene lactone converted to the cyclopropanated lactone. The mixture wascooled to 30° C., quenched with saturated NH₄Cl, aqueous layer separatedand the organic layer washed with 200 ml of brine. The organic layer wasthen dried over anhydrous MgSO₄.

The NMR of 5-oxa-bicyclo[14.1.0]heptadecan-6-one is as follows: 0.2 ppm(m, 1H); 0.3 ppm (m, 1H); 0.4 ppm (m, 2H); 0.6-0.8 ppm (d, 1H); 1.2-1.5ppm (d, 13H); 1.7 ppm (s, 3H); 1.8 ppm (m, 2H); 2.1 ppm (s, 1H); 2.3-2.5ppm (m, 2H); 4.0-4.1 ppm (m, 1H); 4.3 ppm (m, 1H).

Example F Preparation of 3-Methyl-6-oxa-bicyclo[13.1.0]hexadecane-7-one

To a dry 200 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 2.9 g of 99%3-Methyl-cyclopentadec-5-enone and 25 ml of Methyl Tertiary Butyl Ether(MTBE) was added. The resulting mixture was stirred for 5 minutes. 21.8ml of 1.1 M Et₂Zn were added via syringe. After the temperature of themixture stabilized, 23 g of CH₂I₂ were added while stirring. In about 60minutes a first sample of the product was taken. The gas chromatographytest indicated that 39.3% of the starting alkene lactone converted tothe cyclopropanated lactone. The mixture was left to age overnight. Nextmorning, the mixture was quenched with saturated NH₄Cl, aqueous layerseparated and the organic layer washed with NaHCO₃. The organic layerwas then dried over anhydrous MgSO₄. The gas chromatography testindicated that 39.3% of the starting alkene ketone converted to thecyclopropanated ketone.

The NMR spectrum of 3-methyl-6-oxa-bicyclo[13.1.0]hexadecane-7-one is asfollows: 0.6 ppm (m, 2H); 0.8 ppm (s, 1H); 0.9 ppm (m, 1H); 1.1 ppm (m,3H); 1.2-1.4 ppm (m, 11H); 1.7 ppm (m, 1H); 2.1 ppm (s, 1H); 2.2-2.4 ppm(m, 2H); 2.5 ppm (m, 1H).

Example G Preparation of Bicyclo[14.1.0]heptadecan-8-one

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 6.7 g of ZnCu,80 ml of Methyl Tertiary Butyl Ether (MTBE) and one iodine crystal wereadded. The resulting mixture was stirred until color faded. 30 g ofCH₂I₂ was added and the mixture was heated to reflux. 22 g of 99% purecyclohexadec-8-one was added dropwise. After the mixture turned grayishpink color, a first sample was taken. The mixture was cooled, quenchedwith 100 ml of saturated NH₄Cl and stirred for 15 minutes. The mixturewas allowed to settle, the aqueous layer was separated, and the organiclayer was extracted with two 50 ml portions of toluene. Toluene wasadded to the crude sample and dried over anhydrous MgSO₄.

The NMR spectrum of bicyclo[14.1.0]heptadecan-8-one is as follows: 0.2ppm (m, H); 0.4 ppm (s, H); 0.6-0.7 ppm (m, H); 1.1 ppm (s, H); 1.2-1.5ppm (m, 10H); 1.6 ppm (m, H); 1.7 ppm (m, H); 1.8 ppm (m, 2H); 2.0 ppm(s, H); 2.2 ppm (m, H); 2.5 ppm (m, H); 2.6 ppm (m, H).

Example H

Incorporation of Bicyclo[13.1.0]hexadecan-4-one into a FragranceFormulation Ingredients Parts Allyl caproate 0.50 Benzyl acetate 130.00Citral 0.50 Citronellol 50.00 Citronellyl acetate 110.00 Coumarin 11.00Bicyclo[13.1.0]hexadecan-4-one 16.00 Damascenone 1.00 Ethyl caproate1.00 Ethyl-2-methyl butyrate 1.00 Geraniol 65.00 Hexenyl acetate, cis-315.00 Hexyl acetate 2.25 Ionone alpha 12.00 Ionone beta 12.00 Iso amylacetate 0.25 Linalool 45.00 Linalyl acetate 130.00 Lyral 30.00 Mandarinoil md ref a lmr 12.50 Methyl anthranilate 30.00 Muskalactone 25.00Nonadienal, trans-2-cis-6 15.00 Orange oil bitter wi 12.50 Orange oilsweet 25.00 Petitgrain 45.00 Phenyl acetaldehyde 2.00 Phenyl ethylalcohol 100.00 Tagette oil egypt md ref a lmr 7.50 Terpineol 80.00Undecalactone gamma 1.00 Vetivert oil haiti md ref a lmr 12.00 Total1000.00

The fragrance formulation was described as having sweet, powdery andfloral tones.

Example I

Incorporation of Bicyclo[14.1.0]heptadecan-8-one into a FragranceFormulation Ingredients Parts 3-Dodecenal, 10% In Dipropylene Glycol25.00 Amyl Salicylate 50.00 Benz Acetate 65.00 Benzyl Cinnamate 35.00Benzyl Salicylate 150.00 Citronellol Coeur 50.00 Cresyl Phen AcetatePara 1.00 Ethylene Brassylate 12.00 Galbaniff 2.00 Geraniol 10.00Bicyclo[14.1.0]Heptadecan-8-One 40.00 Guaiacwood Oil 4.00 HexenylSalicylate, Cis-3 35.00 Hexyl Cinnamic Aldehyde 200.00 Jasmone Cis 3.00Koavol DH 85.00 Lyral 135.00 Methyl Anthranilate 8.00 Muskalactone 10.00Phenyl Ethyl Phenyl Acetate 35.00 Styralyl Acetate 15.00 Veramoss 15.00Ylang Oil 15.00 Total 1000.00

The fragrance formulation was described as having sweet, powdery andfloral tones.

Example K

Incorporation of 9-Oxa-bicyclo[15.1.0]octadecan-8-one into a FragranceFormulation Ingredients Parts Allyl amyl glycolate 1.00 Benzyl acetate10.00 Benzyl salicylate 55.00 Bergamot oil 35.00 Cashmeran 4.00 Cedrenylacetate 20.00 Citronellol 50.00 Coumarin 25.00 Cyclogalbaniff 3.009-oxa-bicyclo[15.1.0]octadecan-8-one 7.50 Damascone, delta 0.40 Ethylvanillin 1.00 Eugenol 40.00 Galaxolide 90.00 Galbanum oil ref a lmr 0.10Geraniol 13.00 Hedione 80.00 Helional 6.00 Heliotropine 20.00 Hexenylsalicylate, cis-3 13.00 Ionone beta 10.00 Iso e super 60.00 Jasmin absegypt lmr 5.00 Lilial 40.00 Linalool 80.00 Linalyl acetate 65.00 Lyral40.00 Methyl anthranilate 8.00 Methyl ionone gamma 55.00 Muskalactone25.00 Olibanum coeur dep 50 pct 6.00 Patchouli oil 35.00 Sandalore 20.00Sanjinol 20.00 Styralyl acetate 10.00 Vanillin 13.00 Veramoss 4.00Vertofix 25.00 Ylang oil 5.00 Total 1000.00

The fragrance was described as having sweet, powdery and floral tones.

1. A method of improving, enhancing or modifying a fragrance formulationthrough the addition of an olfactory acceptable amount of a compound offormula

wherein X is selected from the group consisting of CH and CH₂; Y is asaturated or unsaturated straight or branched hydrocarbon chainconsisting of 1 to 20 carbon atoms; and W is a saturated or unsaturatedstraight or branched hydrocarbon chain consisting of 1 to 20 carbonatoms, with the proviso that the combined number of the carbon atoms inY and W is at least
 5. 2. The method of claim 1, wherein the fragranceformulation is incorporated into a product selected from the groupconsisting of a perfume, a cologne, a toilet water, a cosmetic product,a personal care product, a fabric care product, a cleaning product, andan air freshener.
 3. The method of claim 2, wherein the cleaning productis selected from the group consisting of a detergent, a dishwashingcomposition, a scrubbing compound, and a window cleaner.
 4. The methodof claim 1, wherein the olfactory acceptable amount is from about 0.005to about 10 weight percent.
 5. The method of claim 1, wherein theolfactory acceptable amount is from about 0.5 to about 8 weight percent.6. The method of claim 1, wherein the olfactory acceptable amount isfrom about 1 to about 7 weight percent.
 7. A method of improving,enhancing or modifying a fragrance formulation through the addition ofan olfactory acceptable amount of a compound of


8. The method of claim 7, wherein the fragrance formulation isincorporated into a product selected from the group consisting of aperfume, a cologne, a toilet water, a cosmetic product, a personal careproduct, a fabric care product, a cleaning product, and an airfreshener.
 9. The method of claim 8, wherein the cleaning product isselected from the group consisting of a detergent, a dishwashingcomposition, a scrubbing compound, and a window cleaner.
 10. The methodof claim 7, wherein the olfactory acceptable amount is from about 0.005to about 10 weight percent.
 11. The method of claim 7, wherein theolfactory acceptable amount is from about 0.5 to about 8 weight percent.12. The method of claim 7, wherein the olfactory acceptable amount isfrom about 1 to about 7 weight percent.